AZ31B镁合金氧化石墨烯掺杂钇盐转化膜耐蚀性研究

目的研究一种绿色环保的表面处理方法,以提高镁合金的耐蚀性。方法采用化学浸泡法,以硝酸钇为成膜物质,在AZ31B镁合金表面成功制备一种新型稀土盐转化膜,并以氧化石墨烯为阻隔剂对该转化膜进行复合掺杂。采用扫描电镜(SEM)对膜层的表面形貌进行观察,采用析氢实验和电化学测试对不同试样在3.5%Na Cl溶液中的耐蚀性进行了研究。结果镁合金钇盐转化膜表面平整均一,覆盖良好。氧化石墨烯掺杂后的钇盐膜层表面出现了大小不均一的瘤状物质,膜层完整,未出现裂痕。析氢实验结果显示,经过处理的转化膜试样可以极大地抑制腐蚀反应的发生。由极化曲线可知,钇盐转化膜的存在使镁合金的腐蚀电位发生了明显正移,正移了150 m V;而氧化石墨烯掺杂的钇盐膜层的腐蚀电位相对于掺杂前变化不大,但其腐蚀电流密度是掺杂前的1/28。电化学交流阻抗谱的测试结果显示,氧化石墨烯掺杂钇盐转化膜的电荷转移电阻最大,Rct为2485?·cm2;钇盐转化膜的电荷转移电阻次之,Rct为1224?·cm2。两者的电荷转移电阻相对于未经处理的镁合金都有明显提升。结论钇盐转化膜可以明显提高AZ31B镁合金的耐蚀性,氧化石墨烯的加入可以进一步提高转化膜层的耐蚀性。     

Corrosion resistance,composition and structure of RE chemical conversion coating on magnesium alloy

Golden yellow rare earths chemical conversion coating was obtained on the surface of magnesium alloy by immersing in cerium sulfate solution.The corrosion resistance of RE conversion coating was evaluated using inmersion test and potentiodynamic polarization measurements in 3.5%NaCl solution.The morphologies of samples before corrosion and after corrosion were observed by SEM.The structures and compositions of the RE conversion coating were studied by means of XPS,XRD and IR.The results show that,the con...     

微弧氧化处理对AZ91D镁合金腐蚀行为的影响

采用碱性硅酸盐溶液,在AZ91D镁合金试样表面制得微弧氧化膜,并利用电化学阻抗方法对镁合金及微弧氧化处理试样在3.5%NaCl溶液中的腐蚀行为进行比较研究.结果表明,镁合金经微弧氧化处理后,腐蚀电位和膜层阻抗均有一定程度的提高.但在浸泡过程中,微弧氧化处理试样的电化学参数呈现出不同的变化规律,初期波动较大,后期则逐渐降低,趋向稳定.     

镁合金微弧氧化复合膜研究进展

微弧氧化（MAO）表面处理技术常用于改善镁合金的特定性能,但MAO膜容易产生微孔和微裂纹从而降低镁合金的耐蚀性。为了提高镁合金微弧氧化膜的使用寿命,主要综述了国内外MAO工艺过程调节措施和MAO膜后处理技术的最新研究进展,重点介绍了近年来国内外镁合金MAO复合膜的研究热点。着重介绍了通过工艺过程调节提高镁合金MAO膜长期保护性能的几项措施：通过电参数和电源类型调节协同电解液成分调整提高MAO膜耐蚀性;通过加入电解液添加剂提高MAO电解液稳定性和电导率;利用具有自封孔作用的添加剂可以参与成膜的特点提高MAO膜致密性;通过复合工艺在MAO膜传统封孔后进一步封闭孔隙。此外,详细介绍了包括疏水涂层、化学镀、类金刚石涂层、生物膜涂层等复合膜工艺的研究进展,强调了复合膜不仅耐蚀性高而且具有功能化应用前景：超疏水复合膜对镁基底具有主动的腐蚀保护作用,超疏水膜协同MAO膜可以提高表面的疏水性;镀镍层致密无微孔且与MAO膜交错咬合能够改善镁MAO膜的导电性和耐蚀性;MAO涂层代替金属缓冲层能够提高类金刚石涂层和基体界面结合强度;生物复合涂层不仅耐蚀性高还具有促进细胞增殖和分化生物活性的作用。最后,基于镁...     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

Corrosion electrochemical behaviors of silane coating coated magnesium alloy in NaCl solution containing cerium nitrate

Sol–gel coatings cannot provide adequate corrosion protection for metal/alloys in the corrosive environments due to their high crack‐forming potential. This paper demonstrates the possibility to employ cerium nitrate as inhibitor to decrease the corrosion development of sol–gel‐based silane coating on the magnesium alloy in NaCl solution. Cerium nitrate was added into the NaCl solution where the silane coating coated magnesium alloy was immersed. Scanning electron microcopy (SEM) was used to examine surface morphology of the silane coating coated magnesium alloy immersed in NaCl solutions doped and undoped with cerium nitrate. The corrosion electrochemical behaviors were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. The results showed that the introduction of cerium nitrate into NaCl solution could effectively inhibit the corrosion of the silane coating coated magnesium alloy. Moreover, the influence of concentration of cerium nitrate on the corrosion inhibition and the possible inhibiting mechanism were also discussed in detail.     

AZ31B镁合金表面微弧电泳复合膜层微观结构及耐蚀性表征

采用微弧氧化技术在AZ31B镁合金表面制备陶瓷层,利用其表面多孔结构借助电泳技术沉积有机膜层,对比研究陶瓷层和复合膜层表面粗糙度、表面及截面形貌、电化学性能及划伤腐蚀特性。结果表明:陶瓷层表面放电微孔被电泳层完全填充并形成均匀膜层,复合膜层表面粗糙度明显降低;微弧电泳复合膜层腐蚀电流密度与陶瓷层和基体相比分别降低2个和4个数量级,极化电阻分别增大2个和4个数量级,腐蚀倾向降低;微弧电泳复合膜层电化学阻值与陶瓷层相比增加4个数量级,同时电容值降低4个数量级,耐蚀性显著提高;由于陶瓷层与电泳层的机械嵌合作用,复合膜层划伤腐蚀过程表现为基体腐蚀及陶瓷层与基体界面的破坏,复合膜层界面处结合完好。     

纯镁表面等离子体电解渗硼与微弧氧化复合膜的制备及耐蚀性

目的 在纯镁表面制备新型复合膜,以提高其耐蚀性.方法 先在硼砂系电解液中对纯镁进行等离子体电解渗硼(PEB)处理,预制表面改性层,然后在硅酸盐系电解液中对其进行微弧氧化(MAO)处理,从而获得PEB+MAO新型复合膜.分别使用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析膜层的微观结构、元素分布及物相组成,膜层的耐蚀性则通过动电位极化曲线和电化学阻抗谱(EIS)来表征.结果 纯镁的等离子体电解渗硼过程经历了电离、置换、吸附和扩散四个阶段,获得的PEB表面改性层由氧化层和扩散层组成.在PEB+MAO复合膜的生长过程中,膜层在其厚度方向存在重叠的现象,而不是逐层的简单堆积.等离子体电解渗透时,硼元素渗入后所形成的渗层区域降低了纯镁基体表面的化学活性,改善了其微观组织结构,进而使PEB+MAO复合膜的腐蚀电流密度较基体、单一PEB改性层和单一微弧氧化膜层分别降低了3、2、1个数量级.同时,EIS研究也表明,PEB+MAO复合膜可以提供相对较长时间的抗蚀保护.另外,分析了PEB表面改性层的生成机理以及PEB+MAO复合膜的形成过程,并建立了物理模型.结论 PEB预处理会显著影响PEB+MAO复合膜的厚度、致密性及成分,继而明显提高纯镁的耐蚀性.该新型的复合膜制备方法有望进一步推广到镁合金上,以提高其耐蚀性和承载能力.     

投料顺序对镁合金表面层状双金属氢氧化物涂层性能的影响

为了考察不同投料顺序对镁合金表面层状双金属氢氧化物(LDHs)涂层性能的影响,并得到一种具有较好耐腐蚀能力的镁合金防腐蚀涂层,通过水热合成法采用不同投料顺序在镁合金表面原位沉积LDHs涂层。使用SEM、XRD、EIS、Tafel曲线和直接浸泡的方法,分别对LDHs涂层的表面形貌、结构和耐腐蚀性能进行评估。结果发现,采用不同的投料顺序得到了不同表面形貌、相似结构和不同耐腐蚀能力的LDHs涂层。所有LDHs涂层的自腐蚀电位、自腐蚀电流密度和阻抗模量相对于基底都分别发生了明显的正移、下降和增加,电位正移值约为0.7 V,自腐蚀电流密度降低值达到3~4个数量级,阻抗模量增加约4个数量级。以上结果表明通过控制投料顺序可以得到具有不同表面形貌的LDHs涂层。采用向硝酸铝中添加硝酸镁后调节溶液p H,再加入碳酸钠的投料顺序,得到LDHs涂层在NaCl溶液中的耐腐蚀能力最好。     

微弧表面处理对AZ31B镁合金耐腐蚀及耐腐蚀疲劳性能的影响

采用微弧表面处理技术(微弧氧化MAO和微弧复合MCC)在AZ31B镁合金基体上制备出不同断面结构的防护涂层。通过电化学腐蚀及腐蚀疲劳测试方法,研究了MAO、MCC涂层的电化学腐蚀及腐蚀疲劳性能。结果表明,生长10 min的MAO涂层具有较好的耐电化学腐蚀性能。MAO涂层表面存在微孔和微裂纹,在应力条件下微孔和微裂纹作为疲劳断裂的裂纹萌生点,可加速裂纹的萌生与扩展,使其腐蚀疲劳寿命相较AZ31B合金基体降低了55%。而具有MCC涂层的AZ31B合金试样腐蚀疲劳极限为(64.0±5.4) MPa,比AZ31B合金基体提高了59%。在低应力载荷下(＜80 MPa),微弧复合涂层试样的腐蚀疲劳强度得到明显提高。     

聚苯胺/环氧涂层对AZ91D镁合金耐蚀性能的影响

通过化学氧化法合成本征态及氢氟酸掺杂态聚苯胺(PANI),用红外光谱对其结构进行表征。以环氧树脂为成膜物质,在AZ91D镁合金基体上制备了本征态及氢氟酸掺杂的 PANI/环氧涂层,用EIS方法研究涂层在3.5%NaCl溶液中的耐蚀性,并用SEM对浸泡后基体表面形貌进行观察。实验结果表明,与环氧清漆相比,本征态PANI的加入明显改善了环氧涂层的耐蚀性,而氢氟酸掺杂后进一步提高了PANI/环氧涂层的性能。用XPS对基体表面分析,发现添加聚苯胺的涂层在镁合金表面形成了具有保护作用的产物膜。     

Corrosion resistance and molecular dynamics behavior of the MAO/SAM composite coatings on magnesium alloy

To improve corrosion resistance of magnesium alloy AZ91D, y-Mercaptopropyltrimethoxysilane (MPTS) was assembled on the surface of micro-arc oxidation (MAO) treated magnesium alloy by self-assembly membrane (SAM) technique. The surface morphology and chemical components of the MAO/SAM composite coatings were analyzed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The corrosion resistance of samples was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy and total immersion tests in a 3.5 wt % NaCl solution. The measured EIS data were simulated by an equivalent circuit. Also the molecular dynamic simulation was used to study the adsorption behavior at the molecular level. The results showed that the surface of magnesium alloy was well covered by the MAO/SAM composite coatings with a better corrosion resistance. Chemical adsorption was formed between the organic molecules and the surface of the MAO coating. The approach presented here afforded an effective alternative for surface modification of magnesium-based materials to meet the many aspects of the application requirements.     

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg−Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation (MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg−Al layered double hydroxide (LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.     

AZ91D镁合金微弧氧化工艺参数的优化

利用自制微弧氧化装置在硅酸盐体系中对AZ91D镁合金进行微弧氧化处理.采用4因素3水平正交试验,从考察膜层厚度、表面粗糙度和耐蚀性出发,确定了AZ91D镁合金在硅酸盐体系中的最佳工艺参数.结果表明：在最佳工艺条件下,微弧氧化膜呈多孔结构、孔径较小,裂纹较少,分布均匀,膜层较为致密;微弧氧化膜由MgO、Mg2SiO4、MgAl2O4和少量的SiO2组成;室温下,在质量分数为3.5%的NaCl中性溶液中浸泡168 h后,膜层表面未出现明显的点蚀现象,耐蚀性较镁合金基体有了很大提高.     

Growth,corrosion and wear resistance of SiC nanoparticles embedded MAO coatings on AZ31B magnesium alloy

In this research, nanocomposite coating was deposited on magnesium matrix AZ31B alloy using the micro arc oxidation (MAO) method. MAO was carried out in SiC-nanoparticles containing suspension using the sodium silicate and sodium aluminate bases at constant current density. The effect of nanopowder addition and MAO periods were also investigated in the present work. Using the Scanning electron microscopy (SEM), the thickness and surface morphology of the coatings were studied. The coefficient of friction and abrasion rate curves were used to analyze nanopowder addition on resistance to abrasion, while the potentiodynamic curves were used for assessing the resistance to corrosion in the ceramic nanocomposite coating deposited on surface of alloy AZ31B. The morphological studies on surface of coatings revealed that the cavitation level and size increases with the increasing coating duration. Besides, Energy Dispersive X-Ray Diffraction (EDS) analyses from cross section and surface of the prepared coatings revealed that nanopowder distribution on interface of coating with matrix and boundaries of the cavities is almost uniform. The cross section studies of the coatings revealed that their thickness increases, as coating duration prolongs. Furthermore, the corrosion behavior of the samples indicated that presence of nanopowder does not significantly affect the resistance to corrosion of the coatings; however, coefficient of friction and abrasion rate of coatings indicates a respective rise and drop in presence of these nanopowders.     

铝合金PEO涂层表面原位制备Mg-Al LDH膜及其耐蚀性能研究

目的优化Mg-Al LDH/MAO涂层的制备工艺,提高铝合金的耐蚀性。方法将微弧氧化样置于不同pH溶液中,在不同反应时间和反应温度下,采用原位生长法在2024铝合金表面制备层间含NO3^–的MgAl-LDHs/MAO复合涂层。借用SEM、EDS、XRD研究LDH/MAO的微观组织结构,并利用电化学法表征MgAl-LDH/MAO复合涂层试样的腐蚀行为,揭示复合涂层的耐蚀机理以及最优异的工艺条件。结果pH值为6和7的溶液制备出的涂层,生成了少量的LDHs,多数集中在孔洞附近,且生长不完全。相比之下,pH值为9的溶液制备出的涂层生成的片状水滑石更多,且较均匀,腐蚀电流较低,腐蚀电位较高。反应时间为12 h时,生成的水滑石较少,只有部分孔洞处会看到一些;反应时间为24 h和48 h制得的合金形貌相差不大,水滑石皆明显多于12 h的样品,且更加均匀。反应温度为180℃和220℃的合金形成的LDHs较多、较均匀,且生长较好,呈现很明显的片状结构。结论弱碱的制备环境、反应温度的升高和反应时间的延长,促进了水滑石的生成,所得Mg-Al LDH/MAO复合涂层有效地改善了2024铝合金的耐蚀性。     

Electrodeposition and corrosion resistance of Ni–P–TiN composite coating on AZ91D magnesium alloy

In order to improve the corrosion resistance and microhardness of AZ91D magnesium alloy, TiN nanoparticles were added to fabricate Ni–P–TiN composite coating by electrodeposition. The surface, cross-section morphology and composition were examined using SEM, EDS and XRD, and the corrosion resistance was checked by electrochemical technology. The results indicate that TiN nanoparticles were doped successfully in the Ni–P matrix after a series of complex pretreatments including activation, zinc immersion and pre-electroplating, which enhances the stability of magnesium alloy in electrolyte and the adhesion between magnesium alloy and composite coating. The microhardness of the Ni–P coating increases dramatically by adding TiN nanoparticles and subsequent heat treatment. The corrosion experimental results indicate that the corrosion resistance of Ni–P–TiN composite coating is much higher than that of uncoated AZ91D magnesium alloy and similar with Ni–P coating in short immersion time. However, TiN nanoparticles play a significant role in long-term corrosion resistance of composite coatings.     

铝合金微弧氧化的研究进展

综述了微弧氧化技术的发展历程、成膜机理,论述了铝合金微弧氧化的特点。基于铝合金微弧氧化工艺研究现状,详细阐述了氧化时间、占空比、电压、电流密度、电解液浓度、基体粗糙度、纳米颗粒添加剂以及复合工艺等对铝合金微弧氧化膜层的组织与性能的影响。如电流密度会影响涂层的生长机理,使膜层的表面结构和内部缺陷产生较大的差异;采用不同的电解液所得到的膜层的厚度和粗糙度有明显的区别;在不同的电压参数下膜层的均匀性及膜层中微孔的尺寸大不相同;制备微弧氧化复合涂层以及采用纳米增强颗粒可使膜层的结构和性能有大幅提升。通过改变以上影响因素对铝合金微弧氧化膜层组织和结构加以调控,从而实现了对膜层性能的优化,如膜层的硬度、耐磨性、耐腐蚀性、抗疲劳性能的提高。最后对铝合金微弧氧化的发展方向提出了展望。     

KOH 对镁合金微弧氧化过程及膜层耐蚀性的影响

在微弧氧化电解液中引入了KOH添加剂,并在镁合金表面制备了陶瓷膜层,研究了KOH浓度对微弧氧化过程中的膜层生长及膜层耐腐蚀性能的影响。结果表明:在镁合金微弧氧化电解液中引入KOH添加剂可以有效降低微弧氧化过程的起弧电压和工作电压,但是KOH浓度过高会使起弧电压增大;KOH的引入会使膜层中的大尺寸孔隙数目减少,孔隙率提高。为了得到较高的膜层生长速率和较好的耐蚀性,电解液中的KOH剂量以1～3 g/L为宜。     

Statistical Process Control

Abstract

In order to improve the corrosion resistance provided by a micro-arc oxidation (MAO) coating on AZ31 magnesium alloy, a polypropylene film was prepared on its surface. Scanning electron microscopy, energy dispersive X-ray analysis and Fourier transform infrared spectroscopy were used to characterise the surfaces of the coatings. The corrosion protective performance of the coatings was evaluated by potentiodynamic polarisation curves, electrochemical impedance spectroscopy and immersion testing. The results show that the microdefects of the MAO coating can be filled by PP and the corrosion resistance of the AZ31 magnesium alloy is improved greatly.